Self-photoinitiating water-dispersible acrylate ionomers and synthetic methods

ABSTRACT

The invention detailed herein comprises a family of novel multifunctional acrylate ionomeric resins, which are water-dispersible, and have built-in photoinitiator. The inventive resins are made self-photoinitiating by their reaction with β-keto esters (e.g., acetoacetates), β-diketones (e.g., 2,4-pentanedione), β-keto amides (e.g., acetoacetanilide, acetoacetamide), and/or other β-dicarbonyl compounds that can participate in the Michael addition reaction as “Michael donors.” These water-dispersible resins cure under standard ultraviolet (UV) cure conditions to give tack-free coatings without the addition of traditional photoinitiators. The present invention further relates to the use of these resins in coatings.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a Divisional of co-pending application Ser. No.10/834,056, filed on Apr. 29, 2004, and for which priority is claimedunder 35 U.S.C. § 119; the entire contents of all are herebyincorporated by reference.

FIELD OF THE INVENTION

The invention detailed herein comprises a family of novelmultifunctional acrylate ionomeric resins, which are water-dispersible,and have built-in photoinitiator. The inventive resins are madeself-photoinitiating by their reaction with β-keto esters (e.g.,acetoacetates), β-diketones (e.g., 2,4-pentanedione), β-keto amides(e.g., acetoacetanilide, acetoacetamide), and/or other β-dicarbonylcompounds that can participate in the Michael addition reaction as“Michael donors.” These water-dispersible resins cure under standardultraviolet (UV) cure conditions to give tack-free coatings without theaddition of traditional photoinitiators. The present invention furtherrelates to the use of these resins in coatings.

BACKGROUND

The information provided below is not admitted to be prior art to thepresent invention, but is provided solely to assist the understanding ofthe reader.

A drawback to the use of initiators or photoinitiators is the productionof volatile low molecular weight fragments that may not beenvironmentally safe.

These resins are characterized by the presence of acrylate groups aspendant moieties and by the ability of these resins to cure understandard UV-cure conditions to give tack-free coatings without theaddition of traditional photoinitiators.

Multifunctional acrylates and methacrylates (“acrylates”) are commonlyutilized in the preparation of crosslinked films, adhesives, foundrysand binders, composite structures, and other materials. Acrylatemonomers and oligomers may be crosslinked by free radical chainmechanisms, which may require any of a number of free radical generatingspecies, such as peroxides, hydroperoxides, or azo compounds, that maydecompose to form radicals either when heated, or at ambienttemperatures in presence of promoters.

An alternative means of initiating reaction is the use of ultraviolet(UV) light or electron beam (EB) radiation to decompose photoinitiatorsto free radicals. For numerous applications, this method offers thepotential of extremely rapid processing because the transformation froma liquid reactive composition to a crosslinked solid is essentiallyinstantaneous upon exposure to UV or EB radiation.

A drawback to the use of initiators to effect free radical reaction, isthat the decomposition of initiators and photoinitiators produces lowmolecular weight fragments that may volatilize during and/or after themanufacturing process. Fugitive emissions create safety issues regardingworkers, consumers, and the environment. For instance, these lowmolecular weight fragments tend to be readily absorbed through skinwhich can cause adverse health effects.

These limitations have been addressed in several key approaches. Thechallenge of fugitive emissions during manufacturing processes orsubsequent leaching of photoinitiator fragments has been attacked bycreating acrylate monomers/oligomers with “built-in” photoinitiators.This may be accomplished by starting with a compound which is known tofunction as a photoinitiator (or a suitable derivative) and eitherfunctionalizing it with an appropriate unsaturated group, i.e. acrylateor methacrylate, so as to produce a new compound which functions as bothmonomer/oligomer and photoinitiator, or by “grafting” onto a preformedoligomer/polymer in order to produce a higher molecular weightphotoinitiator.

Regardless of the effectiveness of these methods, they add additionalmanufacturing procedures and costs.

Moreover, these approaches result in resins of low functionality. Lowfunctionality is detrimental to reactivity and final properties, and mayimpose a requirement for external catalyst or initiator to effectcrosslinking.

The photo-polymerizable units of the ionic, UV-curable resins of thepresent invention are provided by the Michael addition of β-dicarbonylcompounds to acrylate acceptors. The Michael addition of acetoacetatedonor compounds to multi-functional acrylate receptor compounds to makecrosslinked polymers has been described in the literature. For example,Mozner and Rheinberger reported the Michael addition of acetoacetates totriacrylates and tetracrylates. (Macromolecular Rapid Communications,16, 135-138 (1995)). The products formed were crosslinked gels. In onesuch reaction, depicted in FIG. 1, Mozner added one mole of trimethylolpropane triacrylate (TMPTA) having three functional groups to one moleof polyethylene glycol (600 molecular weight) diacetoacetate(PEG600-DAA) having two functional groups. (Each acetoacetate“functional group” reacts twice, thus each mole of diacetoacetate hasfour reactive equivalents.) The resulting network is considered“gelled”, or cured, despite the presence of unreacted acrylic functionalgroups. While further reaction can be promoted, this network cannot bemade liquid either with heat or solvent because it is effectivelycrosslinked.

A more recent and effective solution is described in U.S. Pat. Nos.5,945,489 and 6,025,410 to Moy et al and assigned to Ashland, Inc., theassignee of the present application. Such approach involves reactingmultifunctional acrylates with acetoacetates via Michael Addition inratios that yield uncrosslinked, acrylate-functional resins. Theseresins crosslink upon exposure to an appropriate UV source in theabsence of added photoinitiators.

Ultraviolet (UV)-curable waterborne coatings are interesting because oftheir advantages of environmental protection, lower energy consumption,high curing speed, rheological control, and adaptation to spraying.Conventionally, curable aqueous dispersions are obtained by eitherextra-emulsification or self-emulsification. Self-emulsification ofacrylate ionomers is achieved by introducing hydrophilic ionic groupsinto the backbone of curable resins. A balance between dispersibilityand water resistance can be achieved by incorporating some polyethyleneoxide segments into the backbone of the ionic curable resin.

There exists a need for water-dispersible, UV-curable resins thatincorporate the advantages of self-photoinitiation common to Michaelresins.

SUMMARY OF INVENTION

The invention detailed herein describes the synthesis ofwater-dispersible, un-gelled, self-photoinitiating acrylate ionomers bycombining Michael addition technology with conventional acrylate ionomersynthesis.

The present invention provides ionic, UV-curable multifunctionalacrylate Michael resins. In a first embodiment, illustrated in FIG. 2,an ionic moiety is incorporated into the resin as a part of at least oneisocyanate-reactive, hydrophilic monomer polymerized into the resinbackbone. Isocyanate-reactivity is conferred by the incorporation of atleast one chemical moiety selected from the group consisting ofhydroxyl, primary amine, secondary amine, and thiol. The ionic characterof the monomer is conferred by at least one chemical moiety selectedfrom the group consisting of carboxylate, sulfonate, ammonium,quaternary ammonium, and sulfonium. Carboxylate and sulfonate moietiesrender the ultimate resins anionic. Whereas, ammonium, quaternaryammonium, and sulfonium render the ultimate resins cationic.

A second cationic embodiment of the present invention, illustrated inFIG. 3, incorporates a tertiary amine as part of a chain pendent fromthe resin backbone.

The present invention provides oligomers used to synthesize theinventive resins. The present invention provides a backbone-ionic,isocyanate-terminated, urethane oligomer (FIG. 2A) formed from ahydrophilic monomer described above and at least oneisocyanate-terminated urethane oligomer. Each isocyanate-reactivefunctional group of the hydrophilic monomer is urethane-linked to anisocyanate-terminated urethane oligomer.

The present invention provides hydroxy-functional, acrylated Michaeloligomers (FIG. 2B). The inventive Michael oligomer is synthesized froma β-dicarbonyl compound, a hydroxy-functional acrylate and amultifunctional acrylate ester.

Each isocyanate termination of the backbone-ionic,isocyanate-terminated, urethane oligomer (FIG. 2A) is bound in urethanelinkage with a hydroxy-functional, acrylated Michael oligomer (FIG. 2B)to form the inventive backbone-ionic, multifunctional acrylate Michaelresins (FIG. 2C).

An aspect of the present invention provides pendent-ionic Michaeladdition multifunctional acrylate oligomers comprising a β-dicarbonylmonomer having a central methylene carbon; first and secondmultifunctional acrylate monomers Michael added to the methylene carbon,wherein a portion of the pendant acrylate moieties are reacted with asecondary amine yielding tertiary amine groups (FIG. 3).

The anionic Michael resins of the present invention may be dispersed inwater as their trialkylammonium salt (FIG. 2D). Cationic resins fromboth routes 2 and 3 may be dispersed in water as acetate or formatesalts (FIG. 3).

The present invention provides an ionomeric Michael addition resinadmixed with an amount of water.

The present invention provides that water dispersions of the inventiveionomeric Michael addition resin compositions may be further admixedwith at least one additive selected from the group consisting ofpigments, gloss modifiers, flow and leveling agents, and other additivesas appropriate to formulate coatings, paints, laminates, sealants,adhesives, foundry sand binders, and inks.

An aspect of the present invention provides a method of using theinventive resins comprising applying the resin to a substrate, dryingthe resin, and curing the resin. Cure can be achieved by exposure toactinic light or electron beam radiation, either in the presence, orpreferably in the absence of exogenous photo-initiators. Cure may alsobe achieved through the use of traditional free radical generators.

An aspect of the present invention provides a polymerized productcomprising an ionomeric Michael addition resin composition cured with afree radical generator. A further aspect of the present inventionprovides a substrate coated with an ionomeric Michael addition resincomposition.

A further aspect of the present invention provides a method ofsynthesizing a backbone-ionic isocyanate end-capped urethane oligomercomprising providing a resin reactor having a dry atmosphere; providinga polyol to said reactor; providing a hydrophilic monomer having atleast one isocyanate-reactive moiety to said reactor; providing asolvent to said reactor; providing a urethanation catalyst to saidreactor; adding a multi-functional isocyanate; and maintaining thereaction mixture at a reaction-effective temperature.

An aspect of the present invention provides that the pendant tertiaryamine groups of the inventive resins can function as amine synergists topromote cure of the resin.

An aspect of the present invention provides that the inventive,water-dispersible ionomeric compositions cure, under standard UV-cureconditions, to yield tack-free coatings without the addition oftraditional photoinitiators.

According to an aspect of the present invention, a polymerized productis provided. The polymerized product may be any of coatings, paints,laminates, sealants, adhesives, foundry sand binders, inks, or otherproduct depending on the nature of the inventive ionomer and of theadditive or additives that may be included in the final composition.Suitable additives may be selected from the group consisting ofpigments, gloss modifiers, flow and leveling agents, and other additivesas appropriate to the desired formulation.

According to an aspect, the present invention provides methods of usingthe resins and ionomers of the present invention comprising applying theionomers to a substrate, drying, and curing the resins. Application maybe made by any process known to the industry, including, but not limitedto; roll-coating, spray-coating, brush-coating, dip-coating, and electrocoating.

According to an aspect of the present invention, a method of using theinventive ionomer is provided. According to an aspect of the presentinvention, the inventive ionomer is applied to a surface and cured withactinic light in the absence of traditional photoinitiators. Accordingto an aspect of the present invention, the inventive ionomer is mixedwith an external photoinitiator, applied to a surface, and cured withactinic light. According to an aspect of the present invention, theinventive ionomer is mixed with a peroxide or azo-type initiator,applied to a surface, and cured using thermal energy in the presence orabsence of actinic light.

According to an aspect of the present invention, the inventive ionomeris mixed with a suitable additive selected from the group consisting ofpigments, gloss modifiers, flow and leveling agents, and other additivesas appropriate to the desired formulation, applied to a surface, dried,and cured.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic of a representative crosslinked Michael additionresin;

FIG. 2A is a schematic synthesis of a representative carboxylicacid-functionalized isocyanate end-capped urethane oligomer;

FIG. 2B is a schematic synthesis of a representative hydroxy-functionalMichael addition multifunctional acrylate oligomer;

FIG. 2C is a schematic synthesis of a carboxylic acid-functionalizedurethane acrylate Michael addition oligomer representative of thebackbone-ionic resins of the present invention;

FIG. 2D is a schematic of a backbone-ionic anionomer, representing thetrialkylammonium salt of the resin of FIG. 2C; and

FIG. 3 is a schematic of a representative pendant tertiary amine Michaelmultifunctional acrylate oligomer, and of the cationomer, the carboxylicacid salt thereof.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

Examples are provided in the next section to illustrate details of thesynthesis of these novel materials as well as their application incoatings. Specific reaction conditions and reaction parameters for anyliquid oligomeric resin given in the examples are not limiting for theinvention.

The term monomer is herein defined as a molecule or compound, usuallycontaining carbon and of relatively low molecular weight and simplestructure, which is capable of conversion to oligomers, polymers,synthetic resins, or elastomers by combination with other similar and/ordissimilar molecules or compounds.

The term oligomer is herein defined as a polymer molecule consisting ofonly a few similar and/or dissimilar monomer and/or oligomer units.

The term resin is herein defined as an oligomer, which is capable ofconversion to high molecular weight polymers by combination with othersimilar and/or dissimilar molecules or compounds.

The term thermoset is herein defined to be a high molecular weightpolymer product of resins that solidifies or sets irreversibly whenheated. This property is associated with crosslinking reactions of themolecular constituents induced by heat, radiation, and/or chemicalcatalysis.

The term “polyol” refers to a polyhydric alcohol having at least twohydroxyl groups. The present invention comprehends polyols to includediols. A terminal diol is any polyol in which the terminal portions ofthe molecule are hydroxylated.

The term “hydrophilic monomer,” refers to any monomer having at leastone ionic moiety. An ionic moiety is a chemical grouping that is eitherintrinsically charged, or, may become charged by binding or dissociatingan ion in aqueous solution.

An aspect of the invention provides water-dispersible acrylate ionomericcompositions. As herein defined, the term “ionomer” refers to anion-containing oligomer consisting of ionic and nonionic monomer units.The term “ionomer” further refers to a polymer synthesized from ionicand nonionic oligomers. An aspect of the invention provideswater-dispersible acrylate oligomers and compositions containing saidoligomers. The oligomers of the present invention are synthesized from acombination of ionic and nonionic monomers. In the appropriate context,the terms “ionomer” and “ionomeric” refer to those oligomers thatincorporate at least one ionic monomer. A further aspect of the presentinvention provides polymeric coatings polymerized from the ionomericoligomers of the present invention. In the appropriate context, theterms “ionomer” and “ionomeric” refer to polymers polymerized from atleast one ionomeric oligomer.

An aspect of the present invention provides anionic and cationicionomers, both oligomers and polymers. An “anionomer” is an oligomer ora polymer that contains a chemical group bearing a negative electricalcharge. A “cationomer” is an oligomer or a polymer that contains achemical group bearing a positive electrical charge.

An aspect of the present invention provides a water-dispersible,UV-curable, oligomeric, multifunctional acrylic Michael resincomposition comprising a urethane acrylate, obtained by the reaction ofa backbone-ionic functionalized isocyanate end-capped urethane oligomerwith —OH-containing, self-photoinitiating Michael addition oligomers.

An embodiment of the present invention provides anionomers wherein thebackbone is synthesized from hydrophilic monomers that includecarboxylate or sulfonate groups. An embodiment provides cationomerswherein the backbone is synthesized from hydrophilic monomers thatinclude ammonium, quaternary amine, or sulfonium groups.

A preferred embodiment of the present invention provides anionomerswherein the isocyanate-reactive, hydrophilic monomer incorporated intothe resin backbone is a carboxylic acid.

FIG. 2A presents a schematic of the synthesis of a representativecarboxylic acid-functionalized isocyanate end-capped urethane oligomerused to synthesize the anionomeric resins of the present invention. Thefigure shows a hydroxy-functional carboxylic acid and a polyether orpolyester polyol reacted with a stoichiometric excess ofmulti-functional isocyanate molecules.

The isocyanate-reactive, hydrophilic monomer of the present inventionhas at least one, but may have more than one, isocyanate-reactivemoiety. Non-limiting isocyanate-reactive moieties include hydroxyl,primary amine, secondary amine, and thiol. Hydroxyl is preferred. Inaddition to isocyanate-reactive moieties, the hydrophilic monomer hasionic moieties. A suitable hydrophilic monomer has at least one,preferably has at least two, but may have more than two ionicfunctionalities.

A preferred ionic functionality is an acid. An especially preferred acidis a carboxylic acid. A preferred carboxylic acid monomer isdimethylolpropionic acid. Suitable, non-limiting, hydrophilic monomersinclude bis(hydroxymethyl)butyric acid, N,N-bis(2-hydroxyethyl)glycine,hydroxypivalic acid, malic acid, glycolic acid, and lactic acid.

The isocyanate-terminated urethane oligomer is formed from a centralpolyol monomer and at least two polyisocyanate monomers. Preferably, thepolyol is a terminal diol. Where the polyol has more than two hydroxylgroups, it may react with more than two polyisocyanate monomers to forma branched structure having a plurality of isocyanate terminations. Afirst isocyanate termination of the oligourethane forms a urethanelinkage with one of the isocyanate-reactive moieties on the hydrophilicmonomer. Where the hydrophilic monomer has more than oneisocyanate-reactive moiety, each moiety is urethanated by apolyisocyanate-terminated urethane oligomer.

A hydroxylated, acrylate-terminated Michael oligomer is urethane-linkedto each isocyanate-terminated urethane oligomer. The Michael oligomer isformed from three monomer units. A first monomer is a β-dicarbonylmolecule which has a central methylene carbon. A hydroxyacrylate monomerand a multifunctional acrylate monomer are Michael added to themethylene carbon.

The polyol moiety of the acid-functionalized isocyanate-terminatedurethane oligomer may be a polyether polyol, a polyester polyol, or amixture of polyols. It is preferred that the polyol have a molecularweight in the range of from about 200 to about 5000. More preferably,the polyol has a molecular weight of 1000 to 2000 AMU. The molecularweight of the urethane oligomer is largely a function of the molecularweight of the polyol spacer and of the number of such spacersincorporated into each oligomer.

The polyol may be an alkanediol or a cycloalkanediol. Non-limitingexamples include ethanediol, 1,2- and 1,3-propanediol, 1,2-, 1,3- and1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol,1,4-cyclohexanedimethanol, 1,2- and 1,4-cyclohexanediol and2-ethyl-2-butylpropanediol. Also suitable are diols containing ether orester groups such as diethylene glycol, triethylene glycol,tetraethylene glycol, dipropylene glycol, tripropylene glycol, andpolyethylene glycols, polypropylene glycols, polybutylene glycols orpoly(ethylene glycol adipate)s having a maximum molecular weight ofabout 5000, preferably about 2000 and more preferably about 1000.Reaction products of these diols with a lactone, such as ε-caprolactone,may also be used as diols. A preferred polyol is poly(neopentyl glycoladipate).

The polyol may be a tri- or higher functional alcohol, such as glycerol,trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol orpolyethers started on these alcohols, for example, the reaction productof 1 mole of trimethylolpropane with 4 moles of ethylene oxide

As non-limiting examples of the present invention, carboxylicacid-functionalized isocyanate end-capped urethane oligomers weresynthesized from polyether or polyester polyols having number averagemolecular weights (M_(n)) in the range of from about 200 to about 2000MW.

Carboxylic acid-functionalized isocyanate end-capped urethane oligomers,exemplary of the present invention, were synthesized from aliphaticdiisocyanates in order to minimize absorbance of ultraviolet (UV) lightby chromophores other than the built-in photoinitiator during cure ofthe resin. However, aliphatic, cycloaliphatic, or aromaticpolyisocyanates may be used. Preferred aliphatic diisocyanates include,but are not limited to, dicyclohexylmethane diisocyanate, isophoronediisocyanate (IPDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI),hexamethylene diisocyanate (HDI), hexamethylene diisocyanate trimer(HDT), and IPDI trimer.

FIG. 2B is a schematic of the synthesis of a hydroxyl-containing Michaeladdition oligomer. A β-dicarbonyl Michael donor is reacted withequimolar amounts of a hydroxy-functional acrylate monomer anda-multifunctional acrylate monomer or oligomer in the presence of astrong base. The synthesis of hydroxy-functional acrylate Michaeladdition oligomers is disclosed in co-pending application (serial numbernot yet assigned, Attorney Docket Number 20435/0152) the entire contentsof which is hereby incorporated by reference and for all purposes.

In a preferred embodiment, the β-dicarbonyl Michael donor is aβ-ketoester (e.g., ethyl acetoacetate). Suitably, the present inventionmay also be practiced with a β-diketone (e.g., 2,4-pentanedione), aβ-ketoanilide (e.g., acetoacetanilide), a β-ketoamide (e.g.,acetoacetamide), or a mixture of Michael donors according to the desiredresin quality and end use. In preferred embodiments of the presentinvention, the β-dicarbonyl has functionality (N) wherein N=2.β-Dicarbonyl donors of higher functionality (i.e., N=4, 6 . . . ) aresuitable, but more careful control of reaction stoichiometry must beexercised to avoid unwanted system gelation.

Suitable β-dicarbonyl donor compounds having functionality=2 include,but are not limited to: ethyl acetoacetate, methyl acetoacetate,2-ethylhexyl acetoacetate, lauryl acetoacetate, t-butyl acetoacetate,acetoacetanilide, N-alkyl acetoacetanilides, acetoacetamide,2-acetoacetoxylethyl acrylate, 2-acetoacetoxylethyl methacrylate, allylacetoacetate, benzyl acetoacetate, 2,4-pentanedione, isobutylacetoacetate, and 2-methoxyethyl acetoacetate.

Suitable β-dicarbonyl donor compounds having functionality=4 include,but are not limited to: 1,4-butanediol diacetoacetate, 1,6-hexanedioldiacetoacetate, neopentyl glycol diacetoacetate, cyclohexane dimethanoldiacetoacetate, and ethoxylated bisphenol A diacetoacetate.

Suitable β-dicarbonyl donor compounds having functionality=6 include,but are not limited to: trimethylol propane triacetoacetate, glycerintriacetoacetate, and polycaprolactone triacetoacetates.

A preferred, but not limiting, β-dicarbonyl donor compound havingfunctionality=8, is pentaerythritol tetraacetoacetate.

Preferred hydroxy-functional acrylates include, but are not limited to:2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate, caprolactoneacrylate, propylene glycol monoacrylate, polyethylene glycolmonoacrylate, polypropylene glycol monoacrylate, and mixtures thereof.

Suitable multifunctional acrylate Michael acceptors are chosen fromamong diacrylates, triacrylates, tetraacrylates, and pentaacrylates. Therange of β-dicarbonyl donors and multifunctional acrylate acceptorsaffords the composition designer the opportunity to exercise a greatrange of selectivity in the properties of the final product.

Preferred diacrylates include, but are not limited to: ethylene glycoldiacrylate, propylene glycol diacrylate, diethylene glycol diacrylate,dipropylene glycol diacrylate, triethylene glycol diacrylate,tripropylene glycol diacrylate, tertraethylene glycol diacrylate,tetrapropylene glycol diacrylate, polyethylene glycol diacrylate,polypropylene glycol diacrylate, ethoxylated bisphenol A diacrylate,bisphenol A diglycidyl ether diacrylate, resorcinol diglycidyl etherdiacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate,1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycoldiacrylate, cyclohexane dimethanol diacrylate, ethoxylated neopentylglycol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylatedcyclohexanedimethanol diacrylate, propoxylated cyclohexanedimethanoldiacrylate, epoxy diacrylate, aryl urethane diacrylate, aliphaticurethane diacrylate, polyester diacrylate, and mixtures thereof.

Preferred triacrylates include, but are not limited to: trimethylolpropane triacrylate, glycerol triacrylate, ethoxylatedtrimethylolpropane triacrylate, propoxylated trimethylolpropanetriacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, ethoxylatedglycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritoltriacrylate, aryl urethane triacrylates, aliphatic urethanetriacrylates, melamine triacrylates, epoxy novolac triacrylates,aliphatic epoxy triacrylate, polyester triacrylate, and mixturesthereof.

Preferred tetraacrylates include, but are not limited to:di-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate,ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritoltetraacrylate, dipentaerythritol tetraacrylate, ethoxylateddipentaerythritol tetraacrylate, propoxylated dipentaerythritoltetraacrylate, aryl urethane tetraacrylates, aliphatic urethanetetraacrylates, melamine tetraacrylates, epoxy novolac tetraacrylates,and mixtures thereof.

Preferred pentaacrylates include, but are not limited to:dipentaerythritol pentaacrylate, melamine pentaacrylate, and mixturesthereof.

The Michael addition reaction is catalyzed by a strong base. A preferredbase is diazabicycloundecene (DBU), which is sufficiently strong and isreadily soluble in the monomer mixtures. Other cyclic amidines, forexample diazabicyclo-nonene (DBN) and guanidines are also suitable forcatalyzing this polymerization. Group I alkoxide bases such as potassiumtert-butoxide, provided they have sufficient solubility in the reactionmedium, are typically adequate to promote the desired reaction.Quaternary hydroxides and alkoxides, such as tetrabutyl ammoniumhydroxide or benzyltrimethyl ammonium methoxide, comprise another classof preferred base catalysts to promote the Michael addition reaction.Finally, strong, organophilic alkoxide bases can be generated in situfrom the reaction between a halide anion (e.g., quaternary halide) andan epoxide moiety. Such in situ catalysts are disclosed in pendingapplication Ser. No. 10/255,541 assigned to Ashland, Inc., the assigneeof the present application. The entire contents of application Ser. No.10/255,541 is specifically incorporated by reference in its entirety andfor all purposes.

FIG. 2C sketches the synthesis of a carboxylic acid-functionalizedurethane acrylate, a non-limiting exemplar of the present invention.Each terminal isocyanate group of a carboxylic acid-funtionalizedisocyanate end-capped urethane oligomer, from FIG. 2A, is reacted toform a urethane link with one equivalent of a hydroxyl group-containingMichael addition oligomer, from FIG. 2B.

The isocyanate addition reaction may be accelerated by addition of asuitable catalyst, including, but not limited to triethylamine,1,4-diazabicyclo[2.2.2]octane, tin dioctoate or dibutyltin dilaurate.Preferred catalysts include tin dioctoate and dibutyltin dilaurate.

The invention further provides pendent cationic acrylate oligomerscomprising an ungelled, uncrosslinked Michael addition oligomer havingpendant acrylic functional groups, wherein a portion of said groups arederivatized with a secondary amine. The secondary amine may be a dialkylamine, dialkenyl amine, cycloaliphatic amine, heterocyclic amine,functionalized secondary amine, and compounds with a plurality ofsecondary amine functional groups, such as piperazine. The secondaryamine may comprise a nitrogen covalently linked to two organic radicals,wherein each radical is selected from the group consisting of linear andbranched alkyl, linear and branched alkenyl, and linear and branchedalkynyl. The two carbon radicals may cyclize with the nitrogen to form aheterocyclic ring.

A further embodiment of the present invention provides oligomers inwhich at least one ionic group is attached by a chain pendant from theoligomer backbone. FIG. 3 shows the synthesis of a representativependant tertiary amine-containing Michael addition multifunctionalacrylate oligomer. The oligomer comprises a β-dicarbonyl monomer havinga central methylene carbon and first and second multifunctional acrylatemonomers Michael added to the carbon. Each incorporated multifunctionalacrylate monomer residue has at least one pendant acrylate group.

Suitable and preferred β-dicarbonyl monomers are as described above forbackbone-ionic resins.

Suitable and preferred multifunctional acrylate monomers are asdescribed above for backbone-ionic resins.

The Michael addition reaction is as described above.

The cationomer is formed as sketched in FIG. 3. A pendant tertiary amineMichael addition multifunctional acrylate oligomer is admixed with anacid to form a salt thereof. At least about 1 equivalent ofwater-compatibilizing acid is mixed with the pre-cationic oligomer forneutralizing the amine groups. Non-limiting examples of suitable protondonating organic and inorganic acids include phosphoric, sulfuric,hydrochloric, acetic, formic, and lactic. A preferred acid is acarboxylic acid. Non-limiting, preferred carboxylic acids include formicand acetic. Preferred acids are those (such as, but not limited to,formic and acetic acids) that readily volatilize from the emulsion as itis dried. This yields a neutral cured resin coating that has good waterresistance.

The invention comprehends bridged forms of the resin of FIG. 3 linkedthrough a common tertiary amine nitrogen atom. Two equivalents of theresin of FIG. 3 are reacted with one equivalent of a primary amine. Apendant acrylate moiety from each resin unit adds to the primary amineto form a tertiary amine. The invention comprehends higher-orderoligomers. As the ratio of primary amine to resin is varied, a mixtureof bridged lower- and higher-order oligomers may be formed.

In an embodiment, ionomers are formed from the resins by combining witha counter-ion in an aqueous solution. Water and counter-ion may be addedin any order. As appropriate to the charge of the resin, a counter-ioncome from a weakly basic tertiary amine (pK_(b) of from about 2.5 toabout 9.0) or a weak acid (pK_(a) of from about 5.0 to about 3.0), suchas formic or acetic. Preferably, the counter-ion is readily able todissociate or associate with other ions present to form neutral,volatile compounds at the operating temperatures commonly associatedwith the anticipated use of the resins. Persons of skill in the chemicalarts readily appreciate that Kovats index is a descriptor relating tothe molecular size and boiling point of a compound and therefore, theindex is a measure of the relative volatility of a compound. Persons ofskill recognize that determination of Kovats index is simply performedby gas chromatography.

The inventive ionomers are dispersed in water at a solids loading offrom about 10% to about 75% prior to application to a substrate. Apreferable loading is from about 20% to about 60%. A more preferredloading is from about 30% to about 40%. The loadings are calculated on aweight basis. After application, the ionomers may be dried and cured.

The inventive resins may be admixed with at least one additive selectedfrom the group consisting of pigments, gloss modifiers, flow andleveling agents and other additives as appropriate to formulatecoatings, paints, laminates, sealants, adhesives, foundry sand binders,and inks.

The properties of the inventive ionomeric systems may be engineered bytailoring the reactants. The Michael donor and the multifunctionalacrylate monomer may be varied in conjunction with a hydroxylated (—OHcontaining) acrylate such as 2-hydroxyethyl acrylate (HEA) for thesynthesis of —OH containing Michael addition oligomer. The molecularweight of the polyol, its molecular composition, the stoichiometry ofthe hydrophilic monomer, and the type of multi-functional isocyanateused in the reaction also regulate the properties of the final material.The ability of these materials to form tack-free coatings with goodproperties in absence of photo-initiator has also been demonstrated.

EXAMPLES

Ultraviolet light photo-polymerization was demonstrated by applying aportion of the inventive composition to a surface. The composition wasspread over the surface to a thickness of up to about 3 mils. The resinswere applied to aluminum or stainless steel substrates by the “drawdown” technique. Specimens were cured with a Fusion Systems Corp. UVcuring unit using a 600-watt H-bulb and a belt-speed of 40 feet/minutewhich delivers a UV dosage of ˜840 mJ/cm².

Coating performance properties were measured by a variety of differenttest methods familiar to persons of skill in the art.

Solvent Resistance. Solvent resistance is the ability of a coating toresist solvent attack or film deformity. Rubbing the coating with acloth saturated with an appropriate solvent is one way to assess when aspecific level of solvent resistance is achieved. Rubbing tests wereconducted using either methyl ethyl ketone (MEK) or water (as indicated)and employed a double rub technique, one complete forward and backwardmotion over the coated surface. To normalize test strokes, cheeseclothwas fixed to the round end of a 16-oz. ball peen hammer. The double rubtechnique utilizes the weight of the hammer as the operator holds thehammer at the base of the handle. This test was performed until thedouble rubbing action cut into the film or a noticeable film disorderwas evident. The method is modified from the procedure of ASTM D4752.

Adhesion testing was performed by the crosshatch method on rigidsubstrates using a modified method of ASTM D3359 by Test Tape Method B,using a 6-bladed cutting tool with 3.0 mm spacings. Test tape used wasTesa 4970. The ASTM test reports values from 0B to 5B, with 0B being atotal failure, and 5B characterizing excellent adhesion.

Example 1 Synthesis of OH-Containing Michael Addition Resin I

Trimethylolpropane triacrylate (135.54 g, 0.4574 mole), 2-hydroxyethylacrylate (53.11 g, 0.4574 mole), ethyl acetoacetate (54.11 g, 0.0307mole), tetra-n-butylammonium bromide (2.41 g, 0.0075 mole), and glycidylmethacrylate (9.71 g. (0.0746 mole) were placed into 500 ml glassreactor. The reactor was capped with a cover equipped with mechanicalstirrer, reflux condenser, and temperature monitoring thermocouple. Themixture was allowed to react, with stirring. Heat was applied in orderto bring the temperature to 80° C. over a period of 50 minutes. Thereaction mixture was then maintained at 80° C., for a period of fivehours, until a constant refractive index (1.4796) was attained. Thereaction mixture was cooled to 50° C. and 2.35 g. (0.0112 moles)ethylene glycol methacrylate phosphate (Ebecryl® 168, Trademark UCB) wasadded to quench the catalyst system. The reaction mixture was stirred at50° C. for 15 minutes. The resin obtained had refractive index of1.4796, a viscosity of 593 cP at 50° C., and an OH number of 109 mgKOH/g.

Example 2 Synthesis of Polyurethane Acrylate Ionomer I

Polypropylene glycol (121.79 g, 0.0622 mole; Pluracol® P2010, hydroxylnumber=57.3, nominal molecular weight 2000) (Pluracol trademark BASFCorporation), dimethylolpropionic acid (16.67 g, 0.124 mole), 133.17grams of acetone, and 0.24 grams of dibutyltin dilaurate were placedinto a 1000 ml glass reactor. The reactor was capped with a coverequipped with mechanical stirrer, reflux condenser, temperaturemonitoring thermocouple, and an addition funnel. The funnel was fittedwith a pressure-equalizing sidearm filled with 55.48 g. (0.2488 mole)isophorone diisocyanate (IPDI). The system was flushed thoroughly withdry nitrogen and maintained under a dry nitrogen blanket. The reactorcontents were stirred and heated to raise the temperature to 45° C. overa period of 20 minutes. While holding the temperature at 45° C., theIPDI was added dropwise over one hour. Following addition of the IPDI,the temperature was raised to 60° C. over three hours. The reactionmixture was held at 60° C. until reaching an end point of 1.72% NCO (22hours). The OH-Containing Michael Addition Resin I from Example 1 (72.65g., 0.1244 mole) was then added gradually over ten minutes and themixture was stirred and heated further. Phenothiazine (0.01 g) was addedduring this stage to prevent gelation. The reaction was monitored byFTIR. When the intensity at 2300 cm⁻¹ (—NCO band) attained a constantminimum (after 18 hours), the acetone was removed by vacuum distillationat 60° C. to a pressure of 40 mm Hg. The temperature of the resultingviscous resin was lowered to 45-50° C. and 25.10 g. (0.248 mole)triethylamine was added. After stirring and heating to 55° C. for tenminutes, 400.00 g. of deionized water was added and stirred in for anadditional ten minutes. The product was a viscous translucent liquidcomprising approximately a 40% resin aqueous dispersion. An aliquot ofthe dispersion was further diluted with deionized water to give a 30%aqueous dispersion. Both dispersions were stable when stored in thedark, at ambient conditions, for at least six months.

Example 3 Synthesis of Polyurethane Acrylate Ionomer II

Stage 1. A 1000 ml glass reactor was charged with 236.1 g. (0.476equiv.) poly(neopentyl glycol adipate) (Fomrez 55-112, hydroxylnumber=113.2; Fomrez is a trademark of Witco Chemical), 63.8 g. (0.951equiv.) dimethylolpropionic acid, 238.1 g ethyl acetate, and 0.5 gdibutyltin dilaurate. The reactor was capped with a cover equipped withmechanical stirrer, reflux condenser, temperature monitoringthermocouple, and addition funnel with pressure-equalizing sidearmfilled with 211.5 g. (1.91 equiv.) isophorone diisocyanate (IPDI). Thesystem was flushed thoroughly with dry nitrogen and maintained under adry nitrogen blanket. The reactor contents were stirred and heated to65° C. in 30 minutes. While holding the temperature at 65° C., the IPDIwas added dropwise over 45 minutes. The reaction temperature was thenraised to 80° C. and monitored by FTIR. The reaction proceeded at 80° C.until the intensity at ˜3600 cm⁻¹ (—OH band) was no longer observableand the NCO concentration reached 2.2%.

Stage 2. A 500 ml glass reactor was charged with 170.22 g. (0.08912equiv.) of the Stage 1 product and 46.57 g. (0.09804 equiv.) of the OH—containing Michael Addition Resin I of Example 1. The reactor was cappedwith a cover equipped with mechanical stirrer, reflux condenser, andtemperature monitoring thermocouple. The contents were stirred andheated to 60° C. in 40 minutes and held at that temperature until, asobserved by FTIR, the ˜2300 cm⁻¹ NCO band reached a minimum constantintensity (18 hours). Triethylamine (13.27 g., 0.1311 equiv.) and 419.91g. deionized water were added and the ethyl acetate was removed byvacuum distillation at 380-430 mm. Hg and 60° C. The result was aslightly hazy aqueous dispersion containing about 30% resin, which wasstable with no separation for at least six months at ambient conditionsand away from light.

Example 4 Coating Properties of Polyurethane Acrylate Ionomer II

A film of the 30% aqueous Polyurethane Acrylate Ionomer II of Example 3was drawn down on an aluminum Q Panel (Q-Panel® is a trademark ofQ-Panel Lab Products, Cleveland, Ohio.), dried at 45° C. for 10-15minutes, and cured under a Fusion 600 Watt/in. “H” bulb at 1,000 mJ/cm²UV dose. The resulting clear film was hard and tack-tree. Itsurvived >200 water double rubs and 40 MEK double rubs.

Two formulations of the 30% dispersion of Polyurethane Acrylate IonomerII were prepared as follows: 69% dispersion/31% Hubercarb Q6 calciumcarbonate (Hubercarb is a registered trade name of J.M. Huber,Engineered Materials Sector) and 69% dispersion/31% Zeeospheres W-610(3M Company) for coating commercial wood particle board. Each was drawndown on particle board in two 8-mil thick layers, drying at 50° C. aftereach application. The films were cured as described above to give ˜3.5mils thick, hard films. They exhibited excellent adhesion (0% removal)to substrate by a crosshatch adhesion test.

Example 5 Synthesis of OH-Containing Michael Addition Resin II

A water-soluble triacrylate, SR 9035, (40.5 g, 0.042 moles),2-hydroxyethyl acrylate (HEA) (4.9 g, 0.042 moles), ethyl acetoacetate(EAA) (5 g, 0.385 moles), were added to a 100 mL reactor equipped with amagnetic stirrer and thermocouple. Glycidyl methacrylate(2,3-epoxypropyl methacrylate) 1.01 g, 2% w/w, 0.007 moles) andtetrabutyl ammonium bromide (0.252 g, 0.5 w/w) were added asco-catalysts. High-temperature induced gelation was inhibited by theaddition of a pinch of phenothiazine. The reaction mixture was heated to80° C. with a heating mantle and stirred for 4 h. The reaction yielded aclear, slightly yellow liquid of moderate viscosity. (Viscosity wasmeasured using Brookfield viscometer) The liquid was transferred to anamber colored glass bottle for storage. Carbon-13 NMR confirmed thatabout 97% of the disubstituted EAA product was obtained. This resincured tack-free at ˜200 mJ/cm². However, the coating had very poor waterresistance as measured by water double rubs using standard 1 lb. hammer.

Example 6 Synthesis of Polyurethane Acrylate Ionomer III

A 100 mL resin kettle equipped with a mechanical stirrer and athermocouple was purged with nitrogen for about 2 minutes prior toloading. The purged kettle was charged with polyethylene glycol[MW=200)] (7.5 g, 0.0375 moles), dimethanol propionic acid (1.7 g,0.0125 moles). Three drops of monochlorophenylphosphate were added as awater scavenger to prevent water catalyzed gelation of the urethanereaction Synthesis of urethane oligomers was started by slow addition ofisophorone diisocyanate (IPDI), (22.2 g, 0.1 moles) and dibutyl tinlaurate (2 drops). The exotherm was controlled to below 50° C.Water-soluble triacrylate, SR 9035 (2.4 g), was added to reduce theviscosity of reaction mixture. A pinch of phenothiazine added to preventacrylate gelling at high temperature. At the conclusion of the addition,the resin was maintained under heat until more than 95% of the —OHgroups were consumed as determined by infrared (FTIR) spectroscopy. Atthe end of 2 hours, —OH-containing Michael Addition Resin I, assynthesized in Example 1 (30.65 g, 0.0255 mole), and HEA (3 g, 0.0255mole) were slowly added while maintaining the temperature at about 40°C. The reaction was allowed to continue overnight at room temperature.HEA (˜1 g) and pinch of phenothiazine were added and the reactioncontinued at 40° C. for another hour until less than 2% of the —NCOgroups remained as per FTIR. A sample of the resin was applied to analuminum panel to check coating properties. The remaining resin wasemulsified by stirring with triethylamine (0.6035 g) and water (70 g) togive a 30% dispersion of polyurethane acrylate ionomer. The whitedispersion was stable for a few hours until the onset of phaseseparation.

Example 7 Coating Properties of Polyurethane Acrylate Ionomer III

An aliquot of the product from Example 6 was applied to an aluminumpanel and cross-linked under UV light (600 W/inch “H” bulb lamp at adosage of 840 mJ/cm²). The resin cured to a clear, glossy, tack-freecoating after flashing off the water in an oven. The coating had highsolvent resistance (>200 MEK double rubs) as well as high waterresistance (>200 water-double rubs).

Example 8 Synthesis of Amine-Modified Michael Addition Resin

A 1000 ml. glass reactor was charged with 501.61 g (1.1720 moles) SR 454(ethoxylated trimethylolpropane triacrylate from Sartomer Company),390.66 g. (0.3907 mole) Laromer PE 55 F (polyester diacrylate fromBASF), 78.13 g. (0.6004 mole) ethyl acetoacetate, 4.98 g. (0.0155 mole)tetrabutylammonium bromide, and 19.92 g. (0.1402 mole) glycidylmethacrylate. The reactor was capped with a cover equipped withmechanical stirrer, reflux condenser, and temperature monitoringthermocouple. The stirred mixture was heated to 95° C. in one hour andheld at that temperature until the refractive index of the mixturereached a constant value (1.4862 at 25° C.). Piperidine (4.69 g., 0.0551mole) was then added and the reaction mixture was allowed to cool, withstirring, over 30 minutes to 70° C. The final resin had a refractiveindex of 1.4866 at 25° C. and a viscosity of 18,000 cP at 25° C.

Example 9 Cationic Acrylate Oligomer Emulsion and its Coating Properties

Into a four dram glass vial were weighed 2.00 g. of the Amine-ModifiedMichael Addition Resin prepared in Example 10, 1.00 g. deionized waterand 0.03 g. glacial acetic acid. The mixture was shaken to give a whiteemulsion that remained stable for more than one hour.

A film of the emulsion was drawn down on an aluminum Q Panel, dried at40° C. for 30 minutes, and cured under a Fusion 600 Watt/in. “H” bulb at500 mJ/cm² UVA dose. The resulting clear film was hard and tack-tree. Itsurvived >200 water double rubs and >200 MEK double rubs.

INCORPORATION BY REFERENCE

All publications, patents, patent application publications, and ASTMtest methods cited in this specification are herein incorporated byreference, and for any and all purposes, as if each individualpublication, patent, patent application publication, and/or ASTM testmethod were specifically and individually indicated to be incorporatedby reference. In particular, the entire contents of co-pendingapplication Ser. Nos. 10/628,373, 10/722,478, 10/712,044, 10/682,874,10/836,747, and 11/160,597 are herein incorporated by reference for anyand all purposes. In the case of inconsistencies the present disclosurewill prevail.

1. An ionomer comprising: an ionic, UV-curable Michael resin, an amountof water; and a counter-ion wherein the ionic, wherein the UV-curableMichael resin comprises: at least one hydroxy-functional Michael resinand at least one ionic isocyanate-terminated urethane oligomer whereinsaid at least one hydroxy-functional Michael resin comprises aβ-dicarbonyl monomer, a hydroxy-functional acrylate monomer and amultifunctional acrylate and wherein said at least one ionicisocyanate-terminated urethane oligomer comprises an isocyanate-reactivehydrophilic monomer, a polyol and at least one multifunctionalisocyanate.
 2. The ionomer of claim 1, further comprising at least oneadditive selected from the group consisting of pigments, glossmodifiers, flow and leveling agents and other additives as appropriateto formulate coatings, paints, laminates, sealants, adhesives, foundrysand binders, and inks.
 3. A polymerized product comprising the ionomeraccording to claim 1, cured with a free radical generator.
 4. Thepolymerized product, according to claim 3, wherein said free-radicalgenerator is actinic light.
 5. The polymerized product, according toclaim 3, wherein said free-radical generator is electron beam radiation.6. The polymerized product, according to claim 3, wherein saidfree-radical generator is a peroxide.
 7. The polymerized product,according to claim 6, wherein said peroxide is selected from the groupconsisting of methyl ethyl ketone peroxide (MEKP), tert-butylperbenzoate (TBPB), cumyl peroxide, and t-butyl peroxide.
 8. Thepolymerized product, according to claim 3, further comprising at leastone additive selected from the group consisting of pigments, glossmodifiers, flow and leveling agents and other additives as appropriateto formulate coatings, paints, laminates, sealants, adhesives, foundrysand binders, and inks.
 9. A method of utilizing an ionic Michael resincomprising: providing a substrate; applying the ionomer of claim 1 tosaid substrate; and curing said resin.
 10. The method of using an ionicMichael resin, according to claim 9, wherein applying comprises acoating method selected from the group consisting of roll-coating,spray-coating, brush-coating, dip-coating, and electrocoating.
 11. Amethod of fabricating a backbone-ionic, UV-curable ionomer comprising:providing a resin reactor having a dry atmosphere; providing a polyol tosaid reactor; providing an isocyanate-reactive, hydrophilic monomer tosaid reactor; providing a urethanation catalyst to said reactor;providing a polyisocyanate to said reactor; maintaining a reactionmixture at a reaction-effective temperature; and providing ahydroxy-functional, multifunctional acrylate Michael oligomer.
 12. Themethod of fabricating a backbone-ionic, UV-curable ionomer, according toclaim 11, wherein a preferred isocyanate-reactive, hydrophilic monomeris dimethylolpropionic acid.
 13. The method of fabricating abackbone-ionic, UV-curable ionomer, according to claim 11, wherein saidurethanation catalyst is selected from the group consisting ofdibutyltin dilaurate, tin(II) octoate, and diazabicyclo[2.2.2]octane.14. The method of fabricating a backbone-ionic, UV-curable ionomer,according to claim 11, wherein providing a hydroxy-functional,multifunctional acrylate d Michael oligomer comprises: providing a resinreactor; providing a polyol multifunctional acrylate monomer to saidreactor; providing a hydroxyacrylate monomer to said reactor; providinga β-dicarbonyl monomer to said reactor; and providing a Michael additioncatalyst.
 15. The method of fabricating a backbone-ionic, UV-curableionomer, according to claim 14, wherein said Michael addition catalystis a strong base that is readily soluble in the monomer mixtures. 16.The method of fabricating a backbone-ionic, UV-curable ionomer,according to claim 14, wherein said Michael addition catalyst isselected from the group consisting of diazabicycloundecene,diazabicyclononene, 1,1,3,3-tetramethyl guanidine, Group I alkoxidebases, quaternary hydroxides and alkoxides, and organophilic alkoxidebases generated in situ from the reaction between a halide anion and anepoxide moiety.
 17. The method of fabricating a backbone-ionic,UV-curable ionomer, according to claim 11, further comprising: adding anamount of water; and optionally adding a counter-ion.
 18. The method offabricating a backbone-ionic, UV-curable ionomer, according to claim 17,further comprising adding at least one additive selected from the groupconsisting of pigments, gloss modifiers, flow and leveling agents andother additives as appropriate to formulate coatings, paints, laminates,sealants, adhesives, foundry sand binders, and inks.
 19. A method offabricating a pendant-ionic, UV-curable ionomer comprising: providing aresin reactor having a dry atmosphere; providing a β-dicarbonyl;providing a multifunctional acrylate; providing a Michael additioncatalyst; and maintaining a reaction-effective temperature.
 20. Themethod of fabricating a pendant-ionic, UV-curable ionomer, according toclaim 19 further comprising: adding an amount of water; and optionallyadding a counter-ion.
 21. The method of fabricating a pendant-ionic,UV-curable ionomer, according to claim 19 further comprising adding atleast one additive selected from the group consisting of pigments, glossmodifiers, flow and leveling agents and other additives as appropriateto formulate coatings, paints, laminates, sealants, adhesives, foundrysand binders, and inks.
 22. An oligomerized pendant-ionic,multifunctional acrylate Michael resin comprising: at least twoequivalents of a pendant-ionic multifunctional acrylate Michael resin;and a primary amine, wherein said amine is disubstituted with saidresin.